358化學(xué)試劑2012年4月化學(xué)試劑,2012,34(4),358~360單乙醇胺磷酸酯的合成尹振晏,李艷云,梁祎(北京石油化工學(xué)院化學(xué)工程學(xué)院,北京102617摘要:以乙醇胺、磷酸為原料,經(jīng)酯化反應(yīng)合成了單乙醇胺磷酸酯。研究了影響反應(yīng)的因素,化了反應(yīng)條件。酯化反應(yīng)的最優(yōu)條件為:n(乙醇胺):n(磷酸)=1.0:1.4,回流反應(yīng)5h。經(jīng)減壓蒸餾除去溶劑烷得粗產(chǎn)品,收率達(dá)94.0%。再用90%乙醇純化得目標(biāo)產(chǎn)品?；厥章?5.0%。對目標(biāo)產(chǎn)品進(jìn)行熔點(diǎn)測定、元素分析和紅外光譜表征,可確認(rèn)該產(chǎn)品為標(biāo)題化合物。該產(chǎn)品長期依賴進(jìn)口,該方法已擴(kuò)大試驗(yàn),有待實(shí)現(xiàn)工業(yè)化。關(guān)鍵詞:單乙醇胺磷酸酯;乙醇胺;磷酸;酯化;合成中圖分類號:TQ423文獻(xiàn)標(biāo)識碼:A文章編號0258-3283(2012)04-0358-03單乙醇胺磷酸酯是一種新型的家畜飼料添加學(xué)純,北京化工廠)。劑,屬磷酸酯類。國外很早有過研究,但未見1.2反應(yīng)過程工業(yè)化報(bào)道;目前國內(nèi)研究較少,至今未見任何報(bào)在裝有電動攪拌器、溫度計(jì)、分水器接冷凝管道。單乙醇胺磷酸酯也是一種重要的陰離子表面的500mL三口瓶中加入150mL癸烷溶劑及活性劑,可廣泛應(yīng)用于化纖、紡織、皮革、塑料造80.7g(0.7mol)85%的磷酸,在10℃以下滴加紙、化妝品等工業(yè)領(lǐng)域。它具有優(yōu)良的抗靜電30.5g(0.5mol)乙醇胺,不斷攪拌,滴完后加熱性與乳化分散性,并有潤滑、洗凈、耐酸堿等特性,回流反應(yīng)5h,分出反應(yīng)生成的水,最后經(jīng)減壓蒸在化妝品領(lǐng)域越來越受到重視。據(jù)文獻(xiàn)[69報(bào)出溶劑,冷卻,加入50mL乙醇,攪拌,再移至錐形道,合成其他乙醇胺磷酸酯的工藝路線較多,利用瓶中,冷卻結(jié)晶,抽濾,得66.3g粗品,收率不同的合成條件和磷酸酯化試劑得到的產(chǎn)物性能94.0%;再經(jīng)90%乙醇重結(jié)晶,收率95.0%差別很大。本文采用磷酸為磷酸酯化試劑合成磷m.p.234237℃(文獻(xiàn)值:234~238℃)。元酸酯,與經(jīng)典的三氯氧磷、五氧化二磷為磷酸酯化素分析,實(shí)測值(計(jì)算值),%C17.43(17.40);h5.56(5.58);n8.98(9.01)試劑相比原料穩(wěn)定性高,毒性低工藝簡單溶劑循環(huán)利用、無污染,具有廣泛的應(yīng)用前景。其合成2結(jié)果與討論路線如下所示。2.1正交方案及結(jié)果從對反應(yīng)的分析以及實(shí)驗(yàn)的初步摸索,考察0ch2-ch2O--p--+H2原料物質(zhì)的量比反應(yīng)時間溶劑用量等因素對反應(yīng)的影響,選用三因子三水平正交實(shí)驗(yàn)。三因子 OH三水平正交實(shí)驗(yàn)方案如表1所示。表1正交實(shí)驗(yàn)方案FR-750傅里葉變換紅外分光光度計(jì)(美國因子1實(shí)驗(yàn)部分 ab. Program of orthogonal experiment1.1主要儀器與試劑,3An(乙醇胺):n(磷酸)1.0:1.21.0:1.41.0:1.6 Nicolet公司); Flash EA1112元素分析儀(美國熱B反應(yīng)時間/4.05.06.0電公司);XTA顯微熔點(diǎn)測定儀(北京電光科學(xué)C溶劑用量/mL150200250儀器廠);SXHW調(diào)溫型電熱套(河北省黃驊市新興電器廠);SH2-D循環(huán)水式真空泵(鞏義市英峪予華儀器)。收日:2010708作者介:尹振晏(1963-),男,河北石家莊人本科,則教乙醇胺(化學(xué)純,成都化學(xué)試劑廠);85%磷授主要從事生物質(zhì)及精細(xì)化工等方面的研究。酸(化學(xué)純,上海試劑一廠);無水乙醇、癸烷(化通訊作者:李艷 E-mail liyanyun biptduc第34卷第4期尹振晏等:單乙醇胺磷酸酯的合成359正交實(shí)驗(yàn)結(jié)果見表2。2.5重結(jié)晶溶劑的選擇表2正交實(shí)驗(yàn)結(jié)果該產(chǎn)品易溶于水,但結(jié)晶困難,而在大多數(shù)有 Tab.2 The result of orthogonal experiment機(jī)溶劑中溶解度又很小,所以給產(chǎn)品的純化造成實(shí)驗(yàn)號A收率/%一定的困難,經(jīng)多次試驗(yàn)最后確定:90%乙醇為最B1274.5好,實(shí)驗(yàn)結(jié)果如表3所示。2C123274.5表3不同試劑中重結(jié)晶的結(jié)果368.8 Tab.3 The recrystallized result of different reagents312312346.1重結(jié)晶試劑無水乙醇90%乙醇水丙酮異丙醇22233323131292.2產(chǎn)品回收率/%85.595.050.380.184.2685.1產(chǎn)品性狀加熱溶,易溶,不溶,不溶,754.6仍不溶易結(jié)晶結(jié)晶困難發(fā)粘發(fā)粘867.410制進(jìn)行重是驗(yàn)進(jìn)行結(jié)注:取10.0g產(chǎn)品溶于10mL溶劑中進(jìn)行重結(jié)晶實(shí)驗(yàn)進(jìn)行結(jié)960.3果比對。M217.80175.20227.00y平均=69.28180.90由表3結(jié)果可見,選擇90%乙醇作為重結(jié)晶M2223.40234.10M,182.30214.20215.60y總值=623.5試劑效果最好。m72.60058.40075.667m274.46778.03360.3003產(chǎn)品IR表征結(jié)果m,60.76771.40071.867將純化所得產(chǎn)品進(jìn)行紅外光譜分析,譜圖見.038s0.03310.05980.0384圖1所示,各官能團(tuán)特征吸收峰分析如下。因?yàn)閷τ诋a(chǎn)物來說收率越高越好,因此從計(jì)算出的M得出A2、B2、C1最好。由公式算出的本實(shí)驗(yàn)中各S的值可以看出:S2>S3>S1(故表明各因子A、C、B對結(jié)果的影響依次減小);磷酸酯25化反應(yīng)的最優(yōu)工藝條件為:A2B2C1,即原料物質(zhì)的量比為:n(乙醇胺):n(磷酸)=1.0:1.4,反應(yīng)4000300020001000 vlem"時間5h,150mL癸烷溶劑。圖1產(chǎn)品的1R譜圖2.2原料物質(zhì)的量比對酯化反應(yīng)的影響 Fig.1 IR Spectrum of product反應(yīng)為酯化反應(yīng),一般需采用酸催化,所以磷在2906.2cm-1附近為飽和烴的C—H彎曲酸既是催化劑又是酯化試劑,在反應(yīng)過程中其用振動吸收;2694.1、2642.0cm附近為CH2一量應(yīng)適當(dāng)增加,試驗(yàn)結(jié)果表明:原料物質(zhì)的量比為CH2的對稱伸縮振動吸收;1452.1cm處為Cn(乙醇胺):n(磷酸)=1.0:1.4為最佳,磷酸過H變形振動吸收;1162.9cm附近存在P一0的少反應(yīng)不充分,過多則難以去除,也增加成本。振動吸收峰;1085.7和1031.7cm附近為P一2.3加料溫度的影響0—C的伸縮振動吸收;765.6cm處有較穩(wěn)定的磷酸酯化反應(yīng)對溫度的要求很高,而且該反弱吸收峰說明分子中含有多個CH2基團(tuán)。應(yīng)放熱顯著,所以在滴加乙醇胺的過程中需保持由此證實(shí)了產(chǎn)品為預(yù)期結(jié)構(gòu)的磷酸酯產(chǎn)物。較低溫度,以促進(jìn)酯化反應(yīng)順利進(jìn)行,經(jīng)實(shí)驗(yàn)發(fā)現(xiàn)應(yīng)采取冰鹽浴,控制在10℃以下滴加,而且緩慢4結(jié)論滴加效果較好。以乙醇胺、磷酸為原料,經(jīng)酯化反應(yīng)合成了單2.4反應(yīng)時間的影響乙醇胺磷酸酯。研究了影響反應(yīng)的因素,優(yōu)化了該磷酸酯化反應(yīng)是在常壓下進(jìn)行的,反應(yīng)速反應(yīng)條件,酯化反應(yīng)的最優(yōu)條件為:n(乙醇胺):度較慢,而對于大多數(shù)酯化反應(yīng)來說,增加反應(yīng)時n(磷酸)=1.0:1.4,回流反應(yīng)5h。經(jīng)減壓蒸餾間可使反應(yīng)物的轉(zhuǎn)化率提高,反應(yīng)時間太短反應(yīng)除去溶劑得粗產(chǎn)品,收率達(dá)94.0%用90%的乙不完全,轉(zhuǎn)化率低,但時間過長必然增加成本。經(jīng)醇純化得目標(biāo)產(chǎn)品,收率95.0%試驗(yàn)確定反應(yīng)最佳時間5h為宜。對目標(biāo)產(chǎn)品進(jìn)行熔點(diǎn)測定、元素分析和紅外360化學(xué)試劑2012年4月光譜表征,可確認(rèn)該產(chǎn)品為標(biāo)題化合物。該工藝[9何幼鷺椰油酸單乙醇酞胺磷酸醋的合成與性質(zhì)研究已進(jìn)行了工業(yè)化實(shí)驗(yàn),可基本實(shí)現(xiàn)工業(yè)化。[J]武漢生物工程學(xué)院學(xué)報(bào),2007,3(2):82-84 [10] Kendall Company, Baston, Mass. Method of making 2-參考文獻(xiàn): aminoethyl phosphate: US, 644 603[ P]. 1972-02-22.]EMILIANO V, FERRARI G. Improvents in or relating to[11]閻長泰有機(jī)分析基礎(chǔ)[M].北京:高等教育出版社, the preparation of 2-amino-ethyl-monophosphste:GB,8861999:31.504[p].1962-01-10 [2] CIBA LIMITED. Complete specification. process for the Synthesis of monoethanolamine phosphate YIN Zhen-yan, ineering manufacture of phosphoric acid esters and piperazine and U Yan-yun'", LIANG College of Chemical Enginering, morpholine derivatives: GB, 861 463[ P]. 1961-02-22. Beijing Institute of Petro-Chemical Technology, Beijing3]王志峰飼料磷酸鹽的市場與生產(chǎn)現(xiàn)狀[]四川化工102617, China), Huaxue Shiji,2012,34(4),358-360 Abstract: Monoethanolamine phosphate was synthesized by與腐蝕控制,1999,2(2):4447 anolamine a4]姜萍飼用磷酸鈣現(xiàn)狀與前景[]獸藥與飼料添加 etha ine and phosphoric acid as raw materials through劑,1999,4(1):19-20. esterification. Factors influencing the reactions were invesit5]貢長生磷酸醋類表面活性劑的合成和應(yīng)用[]現(xiàn)at. The experimental conditions were optimized. The opti化工,1996,(9):21-25 mum conditions of the esterification are described as follows n(ethanolamine): n phosphoric acid 1.0: 1.4, refluxed6]張速戎,劉翠華,張艦新型磷酸酯兩性表面活性劑的合成及性能研究[J].北京輕工業(yè)學(xué)院學(xué)報(bào),2000,18 for h, 150 mL decane solvent. The product was obtained(1):22-26. with a yield of 94. 0%. After the product was recrystallized with 90% alcohol, the yield was 95.0%. Then the product【7]陳遠(yuǎn)霞,周海,陳文納,等油酸二乙醇酰胺磷酸酯的 was determined by the analysis of elements IR and melting合成及其防銹潤滑性能研究[】化工技術(shù)與開, od has been magified and industri ndustrialize008,37(3):10-13.8]周富榮,鄧芳月桂酸二乙醇酸胺磷酸醋鹽的合成及 Key words: monoethanolamine phosphate ethanolamine性質(zhì)[].表面活性劑工業(yè),2000,(4):27-29 phosphoric acid; esterification :synthesis(上接第318頁) paration of two novel ditopie ligands derived from Schifr [7] FUSON C, MCKEEVER H. Chloromethylation of aro- base GAO Wei, WANG Qiang'(Engineering Research Center matic compounds J]. Org. React., 1942,1: 63-90.8]劉海彬,王梅新型多溴代水楊醛及其Schif堿配體的8,.cbadeumdho《CkmindChemieIEngncmgchooihmisryandhecalnneng合成與表征[].化學(xué)試劑,2010,32(2):102-104 Wuhan Textile University, Wuhan 430020, China), Huaxue []JIN Chun, FAN Wei-bi, JIA Yin-juan, et al. Encapsula- Shiji,2012,34(4),315-318;360 Abstract: 5-Methyl-3-methyle piperidin salicylaldehyde,5. tion of transition metal tetrahydro-Schiff base complexes in zeolite Y and their catalytic properties for the oxidation bromo-3-methylene piperidine salicylaldehyde and 5-bromo-3. methylene morpholine salicylaldehyde were synthesized. ary amine backbone was prepared from condensation of salicylaldehyde and dieth- [10] DEKKERS J, GOODWIN H A. Tridentates and quadri ylenetriamine and the reduced ct with NaBH, was also Mlate Schiff bases from primary diamines]. Ast.. reported. The stability and hy denta lysis of the metal salt com-m.,19662-250 plex with Schiff base d. The compounds were characterized by NMR, IR and MS. Syothesis of several salicylaldehyde derivatives and pre- Key words: salicylaldehyde derivatives; Salen; ditopic ligand(上接第348頁) limit of detection was 0. 2 mg/ and the limit of quantificationd mobile phase was methanol-0. I mol/L phosphate buffer (pH was 1. 2 mg/L. The method was simple, rapid, accurate a 3)(60: 40): Uv-210 nm detector the flow rate was 1.0 reproducible and good for the determination of trially isocyam/min. The linear range was from1.0to200.0mg/ as the nurate9 related coefficient was 0. 999 9 and the re ecovery as Key words: high performance liquid chromatography; trially 99.33%. The relative standard derivation was 1. 81%,the isocy ocyanurate;determination